Hydrochloric Acid → HCID 86684985, compound

HRID 2176082Notes

Reaction equation

HRID 2176082 reaction equation
Br[C:2]1[CH:21]=[CH:20][C:19]2[C:16]3=[C:17]4[C:18]5[C:9]([C:10](=[O:35])[N:11]([C:23]6[C:28]([CH:29]([CH3:31])[CH3:30])=[CH:27][CH:26]=[CH:25][C:24]=6[CH:32]([CH3:34])[CH3:33])[C:12](=[O:22])[C:13]=5[CH:14]=[CH:15]3)=[CH:8][CH:7]=[C:6]4[C:5]3=[CH:36][CH:37]=[CH:38][C:3]=1[C:4]=23.[NH2:39][C:40]1[CH:45]=[CH:44][CH:43]=[CH:42][C:41]=1[SH:46].C(=O)([O-])[O-].[K+].[K+].Cl>CN1CCCC1=O>[NH2:39][C:40]1[CH:45]=[CH:44][CH:43]=[CH:42][C:41]=1[S:46][C:2]1[CH:21]=[CH:20][C:19]2[C:16]3=[C:17]4[C:18]5[C:9]([C:10](=[O:35])[N:11]([C:23]6[C:28]([CH:29]([CH3:31])[CH3:30])=[CH:27][CH:26]=[CH:25][C:24]=6[CH:32]([CH3:34])[CH3:33])[C:12](=[O:22])[C:13]=5[CH:14]=[CH:15]3)=[CH:8][CH:7]=[C:6]4[C:5]3=[CH:36][CH:37]=[CH:38][C:3]=1[C:4]=23

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 87132-AminothiophenolHCID 11430Potassium CarbonateHCID 11272966HCID 11272966, compound

Product 1

HCID 86684985HCID 86684985, compoundYield 86.3%

Reagents, catalysts & solvents 1

HCID 13387N-methyl-2-pyrrolidoneSolvent

Procedure

Compound 8-bromo-2-(2,6-diisopropylphenyl)-1H-benzo[5,10]anthra[2,1,9-def]isoquinoline-1,3(2H)-dione (9.0 g), 2-aminobenzenthiol (2.19 g, 10% excess) and anhydrous potassium carbonate (1.10 g) were added to 100 mL of N-methyl-2-pyrrolidinone (NMP). The solution was heated rapidly and refluxed for 30 min. After a minute the liquor was added to 2% aqueous hydrochloride acid (750 ml) and after standing overnight, filtered and dried at 105° C. to give a red-blue solid of 8-((2-aminophenyl)thio)-2-(2,6-diisopropylphenyl)-1H-benzo[5,10]anthra[2,1,9-def]isoquinoline-1,3(2H)-dione (8.31 g) with a nominal yield of 86.3%. 8-((2-aminophenyl)thio)-2-(2,6-diisopropylphenyl)-1H-benzo[5,10]anthra[2,1,9-def]isoquinoline-1,3(2H)-dione (5.15 g) was dissolved in warm glacial acetic (31 mL) and concentration hydrochloride acid (3.1 mL) giving a fine suspension. The suspension was cooled to 0° C. and a solution of sodium nitrite (0.6 g) in water (9 mL) added and stirred continuously till clear. The prepared solution was added to a boiling solution of hydrated cupric sulphate (9.7 g) in water (150 mL) with good stirring within 1 hour. After boiling a further 1 hour, the solution was cooled, filtered and a blue solid was given. The solid was washed with a warm solution of sodium hydroxide (50 mL, 3%) three times and purified on chromatography column to eliminate by-products. The blue solid of 2-(2,6-diisopropylphenyl)-1H-thioxantheno[2′,1′,9′:10,5,6]anthra[2,1,9-def]isoquinoline-1,3(2H)-dione (1.82 g) was given with a nominal yield of 36.5%. MS: base peak 587.

Workup

  1. temperatureThe solution was heated rapidly
  2. temperaturerefluxed for 30 min
  3. filtrationfiltered
  4. customdried at 105° C.

Sources & evidence

ORD record
ord-d6839d38ea8b4c79b0e4ece7fa1730ef
Source dataset
uspto-grants-2015_06
Patent number
US09062207B2

Reaction notes

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